WO2007092219A1 - Method for refining non-ferrous metal - Google Patents
Method for refining non-ferrous metal Download PDFInfo
- Publication number
- WO2007092219A1 WO2007092219A1 PCT/US2007/002600 US2007002600W WO2007092219A1 WO 2007092219 A1 WO2007092219 A1 WO 2007092219A1 US 2007002600 W US2007002600 W US 2007002600W WO 2007092219 A1 WO2007092219 A1 WO 2007092219A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bath
- ferrous metal
- containing gas
- oxygen
- lance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/003—Bath smelting or converting
- C22B15/0041—Bath smelting or converting in converters
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/025—Obtaining nickel or cobalt by dry processes with formation of a matte or by matte refining or converting into nickel or cobalt, e.g. by the Oxford process
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/06—Refining
Definitions
- This invention relates to refining non- ferrous metal using oxygen to oxidize impurities in the molten metal .
- a problem which arises in the refining of non-ferrous metal using oxygen to oxidize impurities in the molten metal is the formation of accretions on the surface of the lance from which the oxygen is injected into the refining vessel .
- These accretions comprise solidified material from the headspace of the refining vessel which solidify on the face of the lance due to the relatively cold temperature of the lance which results from water-cooling and the oxygen passing through the lance.
- These accretions disturb the flow of oxygen from the lance causing some of the oxygen to be deflected away from the bath. This has three very detrimental effects. First a significant portion of the oxygen is not delivered to the target area of the molten metal bath resulting in inefficient oxygen usage.
- a method for refining non-ferrous metal comprising:
- oxygen containing gas means a gaseous fluid having an oxygen concentration of at least 25 mole percent.
- flame envelope means a combusting flow around and along one or more gas streams .
- coherent jet means a gas stream which has little or no increase in diameter in its flow direction.
- oxygen containing gas is passed from a lance into the headspace of the refining vessel at a velocity which may be- subsonic, sonic or supersonic but is not more than 3 Mach, preferably not more than 1.5 Mach and is most preferably within the range of from 0.835 Mach to 1.13 Mach.
- a flame envelope around the gas stream proximate the lance face.
- the flame envelope serves to melt solidified material and/or to keep material from solidifying on the lance face and thus aids in the attainment of the beneficial results of this invention, i.e. avoidance of detrimental effects of solidified material buildup on the oxygen lance in oxygen refining practice.
- the flame envelope is formed preferably by providing fuel, such as natural gas or other hydrogen containing fuel , and oxidant, such as oxygen containing gas, from the lance into the vessel headspace.
- the fuel and oxidant are provided respectively from two concentric rings of ports on the lance face around the central nozzle from which the refining oxygen containing gas is provided into the headspace, wherein the fuel is provided from the inner ring with respect to the nozzle and the oxidant is provided from the outer ring.
- a single ring design may also be used.
- the flame envelope provides for a second beneficial effect .
- the flame envelope forms a barrier around and along the oxygen containing gas stream for a portion of the oxygen containing gas stream from the lance to the bath. This barrier keeps refining vessel gases in the headspace from passing into the oxygen containing gas stream.
- the oxygen containing gas stream forms a coherent jet for at least a portion of the distance from the lance to the top surface of the molten metal bath. This enables the oxygen containing gas to impact the bath with greater force and purity than would otherwise be the case and this results in improved contact of the oxygen containing gas with the bath which in turn enables more efficient oxygen reaction with the bath constituents and better overall refining results.
- the application of the flame envelope or flame shroud can allow the oxygen lance to be operated at greater lance to bath distances than would otherwise be the case.
- the method of this invention may be employed to refine many non-ferrous or base metals among which are copper, nickel, lead, zinc and tin. It is understood that there may be small amounts of ferrous metal in the bath of non-ferrous metal refined in the method of this invention.
- the invention is particularly useful for the refining of copper wherein oxygen is employed to react with sulfur in the molten copper to produce sulfur dioxide which is then removed from the copper. It is in conjunction with this particularly preferred application and also with reference to the Drawing that the invention will be further described in detail. [0013] Referring now to the Figure there is shown refining vessel 1 which has a refractory lining 4 and which contains a bath 2 of copper and has a headspace 3 above the bath.
- At least one oxygen lance 10 is employed to provide oxygen containing gas into the headspace .
- Oxygen containing gas within the requisite velocity range is passed out of the lance into headspace 3 to form oxygen containing gas stream 12.
- the oxygen from the oxygen containing gas stream reacts with material in the bath to oxidize that material .
- the oxygen reacts with sulfur in the molten copper bath to form sulfur dioxide which then bubbles out from the bath and is removed from the refining vessel .
- the molten bath is agitated through the injection of a gas 15 from below the surface of the bath through one or more injection devices 14.
- gases which may be employed as mixing gas 15 one can name oxygen, nitrogen, argon, steam and mixtures thereof.
- the injection device 14 may be any suitable injection device such as a tuyere or a porous plug.
- the inert gas flows upward from the injection device in a bubble plume 16 and serves to mix the molten metal bath to counteract stratification and to enhance the efficiency of the refining operation.
- the mixing gas which rises through, the molten metal bath may form a continuous eye of freshly exposed bath material composed of solidified or semi-solidified material 17 on the surface of the bath above the injection device from which the mixing gas was provided into the bath.
- one or more oxygen containing gas lances are positioned such that the oxygen containing gas stream from that lance is directed toward and impacts the agitated area of the bath such as at the eye .
- the coherent jet of oxygen containing gas is not required to penetrate deeply into the bath for improved contact and reaction with the bath and therefore can operate efficiently at low Mach number supply conditions .
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for refining non-ferrous metal wherein a stream of oxygen containing gas is provided from a lance (10) into the headspace (3) of a refining vessel (1) for passage to the molten metal bath (2) within the refining vessel, and a flame envelope (13) is provided around and along the oxygen containing gas stream (12) for a portion of its length, wherein the flame envelope simultaneously serves to keep accretions from forming on the lance face and serves to maintain the oxygen- containing gas stream coherent .
Description
METHOD FOR REFINING NON-FERROUS METAL
Technical Field
[0001] This invention relates to refining non- ferrous metal using oxygen to oxidize impurities in the molten metal .
Background Art
[0002] A problem which arises in the refining of non-ferrous metal using oxygen to oxidize impurities in the molten metal is the formation of accretions on the surface of the lance from which the oxygen is injected into the refining vessel . These accretions comprise solidified material from the headspace of the refining vessel which solidify on the face of the lance due to the relatively cold temperature of the lance which results from water-cooling and the oxygen passing through the lance. These accretions disturb the flow of oxygen from the lance causing some of the oxygen to be deflected away from the bath. This has three very detrimental effects. First a significant portion of the oxygen is not delivered to the target area of the molten metal bath resulting in inefficient oxygen usage. Second, some of the oxygen is deflected to such a degree that it impacts the vessel wall thus reducing the life of the refractory lining of the wall. Third, the lance must undergo more frequent maintenance and replacement. All of these problems increase the cost of the refining process.
Summary Of The Invention
[0003] A method for refining non-ferrous metal comprising:
(A) providing a refining vessel containing a bath of non-ferrous metal and having a headspace above the bath of non-ferrous metal;
(B) passing a stream of oxygen containing gas from a lance at a velocity of not more than 3 Mach into the headspace, and passing the oxygen containing gas stream through the headspace from the lance to the non- ferrous metal bath;
(C) providing a flame envelope around the oxygen containing gas stream for a portion of the distance from the lance to the bath; and
(D) reacting oxygen from the oxygen containing gas stream with material in the bath to oxidize said material .
[0004] As used herein the term "oxygen containing gas" means a gaseous fluid having an oxygen concentration of at least 25 mole percent.
[0005] As used herein the term "flame envelope" means a combusting flow around and along one or more gas streams .
[0006] As used herein the term "coherent jet" means a gas stream which has little or no increase in diameter in its flow direction.
Brief Description Of The Drawing
[0007] The sole Figure is a cross-sectional end view of a non-ferrous metal refining vessel in operation with one preferred embodiment of the refining method of this invention.
Detailed Description
[0008] In the practice of this invention oxygen containing gas is passed from a lance into the headspace of the refining vessel at a velocity which may be- subsonic, sonic or supersonic but is not more than 3 Mach, preferably not more than 1.5 Mach and is most preferably within the range of from 0.835 Mach to 1.13 Mach.
[0009] In addition, in the practice of the method of this invention which enables oxygen refining practice of non-ferrous metal with reduced accretion formation, there is employed a flame envelope around the gas stream proximate the lance face. The flame envelope serves to melt solidified material and/or to keep material from solidifying on the lance face and thus aids in the attainment of the beneficial results of this invention, i.e. avoidance of detrimental effects of solidified material buildup on the oxygen lance in oxygen refining practice. The flame envelope is formed preferably by providing fuel, such as natural gas or other hydrogen containing fuel , and oxidant, such as oxygen containing gas, from the lance into the vessel headspace. Most preferably the fuel and oxidant are provided respectively from two concentric rings of ports on the lance face around the central nozzle from which the refining oxygen containing gas is provided into the headspace, wherein the fuel is provided from the inner ring with respect to the nozzle and the oxidant is provided from the outer ring. A single ring design may also be used.
[0010] In addition to contributing to the attainment of the beneficial result of reduced accretion
formation, the flame envelope provides for a second beneficial effect . The flame envelope forms a barrier around and along the oxygen containing gas stream for a portion of the oxygen containing gas stream from the lance to the bath. This barrier keeps refining vessel gases in the headspace from passing into the oxygen containing gas stream. Thus the oxygen containing gas stream forms a coherent jet for at least a portion of the distance from the lance to the top surface of the molten metal bath. This enables the oxygen containing gas to impact the bath with greater force and purity than would otherwise be the case and this results in improved contact of the oxygen containing gas with the bath which in turn enables more efficient oxygen reaction with the bath constituents and better overall refining results. In addition, the application of the flame envelope or flame shroud can allow the oxygen lance to be operated at greater lance to bath distances than would otherwise be the case.
[0011] The method of this invention may be employed to refine many non-ferrous or base metals among which are copper, nickel, lead, zinc and tin. It is understood that there may be small amounts of ferrous metal in the bath of non-ferrous metal refined in the method of this invention.
[0012] The invention is particularly useful for the refining of copper wherein oxygen is employed to react with sulfur in the molten copper to produce sulfur dioxide which is then removed from the copper. It is in conjunction with this particularly preferred application and also with reference to the Drawing that the invention will be further described in detail.
[0013] Referring now to the Figure there is shown refining vessel 1 which has a refractory lining 4 and which contains a bath 2 of copper and has a headspace 3 above the bath.
[0014] At least one oxygen lance 10 is employed to provide oxygen containing gas into the headspace . Oxygen containing gas within the requisite velocity range is passed out of the lance into headspace 3 to form oxygen containing gas stream 12. A flame envelope, as illustrated by flame envelope 13, surrounds each oxygen containing gas stream for a portion of the distance from the lance to the top surface of bath 2. The oxygen from the oxygen containing gas stream reacts with material in the bath to oxidize that material . In particular, the oxygen reacts with sulfur in the molten copper bath to form sulfur dioxide which then bubbles out from the bath and is removed from the refining vessel .
[0015] Preferably, such as is illustrated in the Figure, the molten bath is agitated through the injection of a gas 15 from below the surface of the bath through one or more injection devices 14. Among the suitable gases which may be employed as mixing gas 15 one can name oxygen, nitrogen, argon, steam and mixtures thereof. The injection device 14 may be any suitable injection device such as a tuyere or a porous plug. The inert gas flows upward from the injection device in a bubble plume 16 and serves to mix the molten metal bath to counteract stratification and to enhance the efficiency of the refining operation. [0016] The mixing gas which rises through, the molten metal bath may form a continuous eye of freshly exposed
bath material composed of solidified or semi-solidified material 17 on the surface of the bath above the injection device from which the mixing gas was provided into the bath. In a particularly preferred embodiment of the invention such as is illustrated in the Figure, one or more oxygen containing gas lances are positioned such that the oxygen containing gas stream from that lance is directed toward and impacts the agitated area of the bath such as at the eye . As a result of the bottom injected mixing gas, the coherent jet of oxygen containing gas is not required to penetrate deeply into the bath for improved contact and reaction with the bath and therefore can operate efficiently at low Mach number supply conditions .
[0017] Although the invention has been described in detail with reference to a certain preferred embodiment, those skilled in the art will recognize that there are other embodiments of the invention within the spirit and the scope of the claims.
Claims
1. A method for refining non-ferrous metal comprising:
(A) providing a refining vessel containing a bath of non-ferrous metal and having a headspace above the bath of non-ferrous metal ;
(B) passing a stream of oxygen containing gas from a lance at a velocity of not more than 3 Mach into the headspace, and passing the oxygen containing gas stream through the headspace from the lance to the non-ferrous metal bath;
(C) providing a flame envelope around the oxygen containing gas stream for a portion of the distance from the lance to the bath; and
(D) reacting oxygen from the oxygen containing gas stream with material in the bath to oxidize said material .
2. The method of claim 1 wherein the non-ferrous metal comprises copper.
3. The method of claim 1 wherein the non-ferrous metal comprises nickel .
4. The method of claim 1 wherein the material in the bath comprises sulfur and the oxygen oxidizes the sulfur to form sulfur dioxide.
5. The method of claim 1 wherein the stream of oxygen containing gas is passed from the lance at a velocity within the range of from 0.835 to 1.13 Mach into the headspace .
6. The method of claim 1 wherein the flame envelope is formed by passing fuel and oxidant into the headspace from the lance around the oxygen containing gas stream and combusting the fuel and oxidant.
7. The method of claim 1 further comprising agitating the bath by injecting a mixing gas into the non-ferrous metal bath from below the surface of the bath, and bubbling said mixing gas up through the non- ferrous metal bath.
8. The method of claim 7 wherein said mixing gas comprises one or more of nitrogen, oxygen, argon and steam.
9. The method of claim 7 further comprising forming a well agitated region of the non-ferrous metal bath above the area where the mixing gas passes up through the non-ferrous metal bath.
10. The method of claim 9 wherein the oxygen containing gas stream impacts the well agitated region of the bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002641087A CA2641087A1 (en) | 2006-02-02 | 2007-01-30 | Method for refining non-ferrous metal |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/345,281 US20070175298A1 (en) | 2006-02-02 | 2006-02-02 | Method for refining non-ferrous metal |
| US11/345,281 | 2006-02-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2007092219A1 true WO2007092219A1 (en) | 2007-08-16 |
Family
ID=38169387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2007/002600 Ceased WO2007092219A1 (en) | 2006-02-02 | 2007-01-30 | Method for refining non-ferrous metal |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20070175298A1 (en) |
| CA (1) | CA2641087A1 (en) |
| WO (1) | WO2007092219A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011103132A1 (en) * | 2010-02-16 | 2011-08-25 | Praxair Technology, Inc. | Copper anode refining system and method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1414769A (en) * | 1973-02-07 | 1975-11-19 | Centre Rech Metallurgique | Converting copper materials |
| US4127408A (en) * | 1975-05-22 | 1978-11-28 | Klockner Humboldt Deutz Aktiengesellschaft | Method for the continuous refinement of contaminated copper in the molten phase |
| US4519588A (en) * | 1983-07-01 | 1985-05-28 | Southwire Company | Molten copper oxygenation apparatus |
| JPS6141729A (en) * | 1984-08-06 | 1986-02-28 | Sumitomo Metal Mining Co Ltd | How to operate a copper converter or cylindrical copper refining furnace |
| US5435833A (en) * | 1993-09-30 | 1995-07-25 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process to convert non-ferrous metal such as copper or nickel by oxygen enrichment |
| EP1041341A1 (en) * | 1999-04-02 | 2000-10-04 | Praxair Technology, Inc. | Multiple coherent jet lance |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1424029A (en) * | 1964-01-06 | 1966-01-07 | Union Carbide Corp | Method and apparatus for introducing a stream of process gas into a bath of molten metal |
| MY110307A (en) * | 1990-11-20 | 1998-04-30 | Mitsubishi Materials Corp | Apparatus for continuous copper smelting |
| PL169695B1 (en) * | 1990-11-20 | 1996-08-30 | Mitsubishi Materials Corp | Continuous copper smelting method PL PL PL |
| US5449395A (en) * | 1994-07-18 | 1995-09-12 | Kennecott Corporation | Apparatus and process for the production of fire-refined blister copper |
| US5658368A (en) * | 1995-03-08 | 1997-08-19 | Inco Limited | Reduced dusting bath method for metallurgical treatment of sulfide materials |
| US5814125A (en) * | 1997-03-18 | 1998-09-29 | Praxair Technology, Inc. | Method for introducing gas into a liquid |
| US7452401B2 (en) * | 2006-06-28 | 2008-11-18 | Praxair Technology, Inc. | Oxygen injection method |
-
2006
- 2006-02-02 US US11/345,281 patent/US20070175298A1/en not_active Abandoned
-
2007
- 2007-01-30 WO PCT/US2007/002600 patent/WO2007092219A1/en not_active Ceased
- 2007-01-30 CA CA002641087A patent/CA2641087A1/en not_active Abandoned
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1414769A (en) * | 1973-02-07 | 1975-11-19 | Centre Rech Metallurgique | Converting copper materials |
| US4127408A (en) * | 1975-05-22 | 1978-11-28 | Klockner Humboldt Deutz Aktiengesellschaft | Method for the continuous refinement of contaminated copper in the molten phase |
| US4519588A (en) * | 1983-07-01 | 1985-05-28 | Southwire Company | Molten copper oxygenation apparatus |
| JPS6141729A (en) * | 1984-08-06 | 1986-02-28 | Sumitomo Metal Mining Co Ltd | How to operate a copper converter or cylindrical copper refining furnace |
| US5435833A (en) * | 1993-09-30 | 1995-07-25 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process to convert non-ferrous metal such as copper or nickel by oxygen enrichment |
| EP1041341A1 (en) * | 1999-04-02 | 2000-10-04 | Praxair Technology, Inc. | Multiple coherent jet lance |
Non-Patent Citations (1)
| Title |
|---|
| BUSTOS A.A., BRIMACOMBE J.K. AND RICHARDS G.G.: "Accretion growth at the tuyeres of a Peirce-Smith copper converter", CANADIAN METALLURGICAL QUARTERLY, vol. 27, no. 1, 1988, pages 7 - 21, XP009085742 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011103132A1 (en) * | 2010-02-16 | 2011-08-25 | Praxair Technology, Inc. | Copper anode refining system and method |
| JP2013519796A (en) * | 2010-02-16 | 2013-05-30 | プラクスエア・テクノロジー・インコーポレイテッド | Copper anode refining system and method |
| US8623114B2 (en) | 2010-02-16 | 2014-01-07 | Praxair Technology, Inc. | Copper anode refining system and method |
| RU2573846C2 (en) * | 2010-02-16 | 2016-01-27 | Праксайр Текнолоджи, Инк. | System and method of copper anode affinage |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070175298A1 (en) | 2007-08-02 |
| CA2641087A1 (en) | 2007-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2011218270B2 (en) | Copper anode refining system and method | |
| KR910009873B1 (en) | Submerged combustion in molten materials | |
| EP0866138B1 (en) | Method for introducing gas into a liquid | |
| KR100486184B1 (en) | Supersonic coherent gas jet for providing gas into a liquid | |
| US20100307196A1 (en) | Burner injection system for glass melting | |
| JPH11217620A (en) | Coherent jet injector lance | |
| EP3058109B1 (en) | Top submerged injection lance for enhanced submerged combustion | |
| AU2014335829A1 (en) | Top submerged injection lance for enhanced submerged combustion | |
| US5658368A (en) | Reduced dusting bath method for metallurgical treatment of sulfide materials | |
| US20080264209A1 (en) | Method and system for injecting gas into a copper refining process | |
| US20070175298A1 (en) | Method for refining non-ferrous metal | |
| CN103026161B (en) | Remove the method and system that in smelting furnace, furnace accretion is piled up | |
| CN215930528U (en) | Converting equipment and continuous copper smelting equipment | |
| ES2405998T3 (en) | Method to produce low carbon steel | |
| US20090229416A1 (en) | Refining Molten Metal | |
| AU702459B2 (en) | Process for melting a charge in an electrical arc furnace |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 2641087 Country of ref document: CA |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 07763072 Country of ref document: EP Kind code of ref document: A1 |